Reactivity of a mixed methyl-aminobenzyl guanidinate lutetium complex towards i PrNCN i Pr, CS 2 and Ph 2 PH.

A heteroleptic terminal alkyl lutetium complex stabilized by a bulky guanidinato ligand, LLu(CH 2 C 6 H 4 NMe 2 - o )(Me)(THF) (1) (L = (PhCH 2 ) 2 NC(NC 6 H 3 i Pr 2 -2,6) 2 ) has been synthesized by the treatment of LLu(CH 2 C 6 H 4 NMe 2 - o ) 2 with AlMe 3 (1 equiv.) via an alkyl-exchange reaction in toluene/THF (4 : 1) solution and fully characterized. The difference in the activities of aminobenzyl and methyl was also proven through their selective reactivity, including complex 1 with one equivalent of DIC, CS 2 and HPPh 2 , to afford complexes LLu[(N i Pr 2 ) 2 CMe](CH 2 C 6 H 4 NMe 2 - o ) (2), L 2 Lu 2 [μ-η 1 :η 2 -S 2 CCHC 6 H 4 NMe 2 - o ][μ-η 2 :η 2 -S 2 CCHC 6 H 4 NMe 2 - o ](THF) (4), and {LLu(Me)[μ-O(CH 2 ) 4 PPh 2 ]} 2 (5), respectively. The subsequent transformations have also been investigated, obtaining complexes LLu[(N i Pr 2 ) 2 CMe][(N i Pr 2 ) 2 C CH 2 C 6 H 4 NMe 2 - o ] (3), {LLu[O(CH 2 ) 4 PPh 2 ][μ-O(CH 2 ) 4 PPh 2 ]} 2 (6) and dimeric lutetium phosphide {LLu[μ-O(CH 2 ) 4 PPh 2 ]} 2 (Me)(PPh 2 ) (7). In addition, the guanidinate bimetallic alkynyl-bridged lutetium complex [LLu(μ-CCPh)] 2 (μ-η 2 :η 2 -PhC 4 Ph) (8) bearing the μ 2 -butatrienediyl group was obtained from the reaction of 1 with PhCCH (2 equiv.). The guanidinate lutetium μ-imido complex [LLu(μ-NPh)(THF)] 2 (10) was also obtained in good yield by the treatment of 1 with PhNH 2 .